TWI647110B - Method for manufacturing laminate - Google Patents

Abstract

The invention is a method for manufacturing a laminate, which is a method for manufacturing a laminate having a laminated film and an adhesive layer. The manufacturing method includes a step of forming the adhesive layer on a side of the laminated film. Laminated film is a laminated film that at least laminates a substrate and a film layer containing at least silicon, and the step of forming this subsequent layer includes the step of forming the laminated film into a strip-shaped continuous laminated original fabric. It is transported in the longitudinal direction, and for the aforementioned laminated film original fabric, in this longitudinal direction, a tension of 0.5N / mm ² or more and less than 50N / mm ² per unit cross-sectional area is added, and laminated here The surface of the film layer of the film raw fabric is laminated to form the adhesion layer.

Description

Laminated manufacturing method

This invention relates to the manufacturing method of a laminated body.

This case was filed on October 9, 2014, claiming priority based on Japanese Patent Application No. 2014-208087 filed by Japan, and applying its contents here.

In recent years, as a light-emitting element used in a display device or a lighting device, an organic electroluminescence element (organic EL element) is being studied. The organic EL element is composed of an anode, an organic light-emitting layer, and a cathode. The anode and the cathode are formed as a light-emitting layer. Electrons injected from the cathode and holes injected from the anode are located between the two electrodes. The organic light emitting layer is combined to generate an exciton, and the exciton emits energy to emit light.

However, when an organic EL element, a light-emitting layer or an electrode is in contact with moisture or oxygen, deterioration of the light-emitting layer or the electrode is caused, and a defective portion of light emission may be generated in the element. Therefore, in an organic EL device including an organic EL element, the periphery of the organic EL element is sealed with a sealing material, and a structure that prevents moisture or oxygen from contacting the organic EL element is adopted.

As such a sealing material for an organic EL device, it is known On the surface of a substrate made of synthetic resin, a gas-barrier film laminated with a gas-barrier layer (thin-film layer) of an inorganic compound and an adhesive layer are laminated (for example, see Patent Document 1).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Unexamined Patent Publication No. 07-153570

Generally, when a large number of film-shaped molded bodies are to be processed, a continuous cloth is used for the film-shaped molded bodies to form a continuous strip (film original cloth), and after the processing, appropriate cutting is performed. However, a large number of manufacturing methods of processed shaped bodies are obtained.

When the above-mentioned laminated body is to be produced by such a manufacturing method, the appearance of the film may be damaged due to the damage of the thin film layer having gas barrier properties or the surface of the adhesive layer, and therefore, improvement is required.

The present invention has been made in view of such circumstances, and it is an object of the present invention to provide a method for producing a laminated body that can suppress the damage of a thin film layer having gas barrier properties or the occurrence of poor appearance.

In order to solve the above-mentioned problem, one aspect of the present invention is to provide a method for manufacturing a laminated body, which is a method for manufacturing a laminated body having a laminated film and an adhesive layer formed on a side of the laminated film, A laminated film is a film layer formed of a base material and the aforementioned base material containing at least silicon and the aforementioned adhesive layer. The laminated film has a continuous laminated film base fabric in which the aforementioned laminated film is continuous in a strip shape. And for the aforementioned laminated film original fabric, in the longitudinal direction, a state where a tension per unit cross-sectional area of 0.5 N / mm ² or more and less than 50 N / mm ² is added to one side of the aforementioned laminated film original fabric. Step, forming the aforementioned bonding layer.

In one aspect of the present invention, it can be used as a method for manufacturing a laminated film raw cloth. The manufacturing method is to use the forming material of the above-mentioned adhesive layer as a continuous adhesive layer raw cloth to form the aforementioned adhesive layer. In the step, the original adhesive layer fabric is transported in the longitudinal direction, and for the original adhesive layer fabric, a tension per unit cross-sectional area of 0.01 N / mm ² or more and less than 5 N / mm ² is added in the longitudinal direction. In a state of being bonded to the laminated film original fabric.

In one aspect of the present invention, the method can be used as a manufacturing method for continuously forming the film layer. The manufacturing method includes continuously transporting the base material into a belt-shaped continuous base fabric and continuously transporting the base material to the base material. The step of forming the aforementioned film layer continuously on the surface of at least one side of the original cloth.

In one aspect of the present invention, it can be used as a plasma CVD manufacturing method for a discharge plasma. The manufacturing method uses the step of forming the aforementioned thin film layer. An AC voltage is applied between the second film-forming roll, which is wound against the first film-forming roll, and the second film-forming roll, and the space between the first film-forming roll and the second film-forming roll, Film forming gas Plasma CVD of plasma.

In one aspect of the present invention, the method can be used as a manufacturing method for transporting the base fabric. The manufacturing method is performed by the discharge plasma, and is performed between the first film forming roller and the second film forming roller. An AC electric field is formed, and an endless tunnel-like magnetic field in which the first film forming roller and the second film forming roller expand in the opposite space is formed at the same time. The first discharge plasma is formed along the tunnel-shaped magnetic field. The step of forming the thin film layer with the second discharge plasma formed around the tunnel-shaped magnetic field is carried out by transporting the base cloth to overlap the first discharge plasma and the second discharge plasma.

In one aspect of the present invention, it can be used as a manufacturing method for adjusting the mixing ratio of the organic silicon compound and oxygen contained in the film-forming gas. The manufacturing method is that the thin film layer contains at least silicon, oxygen, and carbon, and the thin film layer is formed In the step, for the formed thin film layer, the distance from the surface of the thin film layer and the total number of silicon atoms, oxygen atoms, and carbon atoms contained in the thin film layer with respect to the points located at the distance are Silicon distribution curve and oxygen distribution curve showing the relationship between the ratio of the number of silicon atoms (the ratio of the number of silicon atoms), the ratio of the number of oxygen atoms (the ratio of the number of oxygen atoms), and the ratio of the number of carbon atoms (the ratio of the number of carbon atoms). And carbon distribution curve, in a manner that all of the following conditions (i) to (iii) are satisfied, the mixing ratio of the organosilicon compound and oxygen contained in the aforementioned film-forming gas is adjusted: (i) the atomic ratio of silicon, the ratio of oxygen The atomic ratio and the carbon atomic ratio are in a region of 90% or more of the entire film thickness of the thin film layer, and satisfy the condition represented by the following formula (1), (Atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon) ... (1), (ii) the aforementioned carbon distribution curve has at least one extreme value, (iii) the aforementioned carbon distribution The absolute value of the difference between the maximum value and the minimum value of the carbon atomic ratio of the curve is 0.05 or more.

In another aspect of the present invention, it can be used as a manufacturing method in which the absolute value of the difference between the maximum value and the minimum value of the silicon atomic ratio in the silicon distribution curve of the thin film layer is less than 5 at%.

In one aspect of the present invention, it can be used as a manufacturing method for the composition of the aforementioned thin film layer as SiO _x C _y (0 <x <2, 0 <y <2).

That is, the present invention includes the following aspects.

[1] A method for producing a laminated body, which is a method for producing a laminated body having a laminated film and an adhesive layer, the production method includes a step of forming the adhesive layer on a side of the laminated film, the layer The laminated film is a laminated film comprising at least a substrate and a film layer containing at least silicon, and the step of forming the aforementioned adhesive layer includes forming the laminated film into a continuous continuous laminated film cloth in a strip shape, and transporting the laminated film in the longitudinal direction. And, for the aforementioned laminated film original cloth, in the aforementioned longitudinal direction, a tension per unit cross-sectional area of 0.5 N / mm ² or more and less than 50 N / mm ² is added, and the aforementioned laminated film original cloth is laminated. The surface of the thin film layer of the cloth forms the adhesive layer.

[2] The method for manufacturing a laminated body according to [1], wherein the step of forming the aforementioned adhesive layer further includes converting the aforementioned adhesive layer into a continuous adhesive tape original cloth, transporting it in the longitudinal direction, and In the longitudinal direction, a layer original fabric is added with a tension per unit cross-sectional area of 0.01 N / mm ² or more and less than 5 N / mm ² , and the original laminated film original fabric is adhered to the laminated original fabric.

[3] The method for producing a laminated body according to [1] or [2], further comprising a step of forming the thin film layer on a surface of at least one side of the substrate, and a step of forming the thin film layer including The base material is continuously conveyed in a band-like continuous base fabric, and the film layer is continuously formed on at least one surface of the base fabric.

[4] The method for producing a laminated body according to [3], wherein the step of forming the film layer includes forming the first film forming roller by winding the base fabric, and forming the film layer with the first film forming roller. An AC voltage is applied between the second film-forming rolls wound around the base fabric and provided in an opposite manner, and the formation of the film layer occurs in a space between the first film-forming roll and the second film-forming roll. The material is the discharge plasma of the film-forming gas; and the plasma film CVD using the generated discharge plasma is used to form the thin film layer on the surface of the base fabric.

[5] The method for manufacturing a laminated body according to [4], wherein the discharge plasma includes forming an AC electric field between the first film-forming roller and the second film-forming roller while forming the first component. The film roll and the second film-forming roll expand into an endless tunnel-like magnetic field in the opposing space, and apply a first discharge plasma formed along the tunnel-like magnetic field and the surrounding area with the tunnel-like magnetic field. The steps of forming the AC voltage of the second discharge plasma to form a magnetic field and forming the thin film layer are carried by the first discharge plasma and the second discharge plasma in such a manner as to overlap the base fabric.

[6] The method for producing a laminated body according to [4] or [5], wherein the aforementioned thin The film layer includes at least silicon, oxygen, and carbon, and the step of forming the thin film layer includes the distance from the surface of the thin film layer in the film thickness direction of the thin film layer to the formed thin film layer, and The total number of silicon atoms, oxygen atoms, and carbon atoms contained in the thin film layer at the points at the aforementioned distances respectively represents the ratio of the number of silicon atoms, that is, the atomic ratio of silicon, the ratio of the number of oxygen atoms, that is, the atomic ratio of oxygen, The silicon distribution curve, oxygen distribution curve, and carbon distribution curve of the ratio of the number of carbon atoms, that is, the relationship of the number of carbon atoms, are adjusted in a manner that satisfies the following conditions (i) to (iii), and controls the Mixing ratio of organosilicon compound and oxygen: (i) The atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are in a region of 90% or more of the entire film thickness of the thin film layer, and satisfy the condition represented by the following formula (1) , (Atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon) ... (1); (ii) the aforementioned carbon distribution curve has at least one extreme value; (iii) the aforementioned carbon The absolute value of the difference between the maximum value and the minimum value of the carbon atomic ratio of the distribution curve is 0.05at% or more.

[7] The method for producing a laminate according to [6], wherein the absolute value of the difference between the maximum value and the minimum value of the silicon atomic ratio in the silicon distribution curve of the thin film layer is less than 5 at%.

[8] The method for producing a laminated body according to any one of [1] to [7], wherein the composition of the thin film layer is SiO _x C _y (0 <x <2, 0 <y <2).

According to the present invention, it is possible to provide a method for producing a laminated body capable of suppressing damage to a thin film layer having gas barrier properties or occurrence of appearance defects.

1‧‧‧ laminated

1A‧‧‧Laminated original fabric

2‧‧‧ laminated film

2A‧‧‧Laminated film fabric

3‧‧‧ substrate

3A‧‧‧ base cloth

4‧‧‧ film layer

4a‧‧‧Level 1

4b‧‧‧Layer 2

5‧‧‧ curl suppression layer

6, 6A‧‧‧ Adjacent layer

7A‧‧‧ separation membrane

8A‧‧‧ Adhesive film

10‧‧‧Film forming device

11‧‧‧Unwinding roller

12‧‧‧ Winding roller

13‧‧‧ transport roller

17, 18‧‧‧ film forming roller

19‧‧‧Gas supply pipe

20‧‧‧Power supply for plasma generation

21‧‧‧electrode

23‧‧‧ Magnetic field forming device

23a, 24a‧‧‧center magnet

23b, 24b‧‧‧External magnet

24‧‧‧ Magnetic field forming device

60‧‧‧ Coating

100, 200, 300‧‧‧ manufacturing equipment

110‧‧‧The first unwinding roller

120‧‧‧ Winding roller

130‧‧‧The second unwinding roller

140‧‧‧ Laminating roller

141, 142‧‧‧ roller

150‧‧‧ surface treatment device

160‧‧‧coating device

170‧‧‧hardening device

180‧‧‧ transport roller

181, 182‧‧‧ roller

190‧‧‧ cutting device

1000‧‧‧ organic EL device

1100‧‧‧ substrate

1200‧‧‧Organic EL element

1210‧‧‧Anode

1220‧‧‧Cathode

1230‧‧‧Organic light emitting layer

SP‧‧‧ Space

[Fig. 1] It is a schematic diagram showing an example of a laminated body manufactured by the laminated body manufacturing method which is one embodiment of the present invention.

[Fig. 2] It is a schematic diagram showing a thin film layer of a laminated body in a method for manufacturing the laminated body according to an embodiment of the present invention.

[Fig. 3] An explanatory view showing a method for manufacturing a laminated body according to the first embodiment of the present invention.

[Fig. 4] An explanatory diagram showing a method for manufacturing a laminated body according to the first embodiment of the present invention.

Fig. 5 is an explanatory diagram showing a method for manufacturing a laminated body according to a second embodiment of the present invention.

[Fig. 6] Fig. 6 is an explanatory diagram showing a modified example of a method for manufacturing a laminated body according to an embodiment of the present invention.

[Fig. 7] A schematic diagram of an organic EL device using a laminated body manufactured by a laminated body manufacturing method according to an embodiment of the present invention.

FIG. 8 is a graph showing a silicon distribution curve, an oxygen distribution curve, a nitrogen distribution curve, and a carbon distribution curve in the thin film layer of the laminated film 1 obtained in Production Example 1. FIG.

[First Embodiment]

Hereinafter, a method for manufacturing a laminated body according to the first embodiment of the present invention will be described with reference to FIGS. 1 to 4. In addition, in all the drawings below, in order to make the drawing easier to see, the dimensions, ratios, and the like of each component are appropriately changed.

[Laminate]

FIG. 1 is a schematic diagram showing an example of a laminate manufactured by the method for manufacturing a laminate according to this embodiment. The laminated body 1 has an adhesive layer 6 formed on a surface on one side of the laminated film 2 and the laminated film 2.

(Laminated film)

In the laminated body 1 according to this embodiment, the laminated film 2 includes a base material 3, a thin film layer 4 held between the base material 3 and the adhesive layer 6, and a thin film layer provided on the base material 3. The curl suppression layer 5 on the surface on the opposite side of the 4 surface.

That is, one side of the laminated body 1 according to this embodiment has a laminated film 2 and an adhesive layer 6; the laminated film 2 has a substrate 3, a film layer 4, and a curl suppression layer 5; a film layer 4 It is provided between the base material 3 and the adhesive layer 6, and the curl suppressing layer 5 is provided on the surface opposite to the surface on which the thin film layer 4 of the base material 3 is provided.

(Base material)

Examples of the forming material of the substrate 3 include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyethylene (PE) and polypropylene (PP) Polyolefin resins such as cyclic polyolefins; Polyamide resins; Polycarbonate resins; Polystyrene resins; Polyvinyl alcohol resins; Saponifications of ethylene-vinyl acetate copolymers; Polyacrylonitrile resins Acetal resin; polyimide resin; polyether sulfide (PES), if necessary, two or more of these can be used in combination. According to the necessary characteristics such as transparency, heat resistance, and linear expansion, it is better to choose a group composed of polyester resin and polyolefin resin; more preferably, it is selected from PET, PEN, and cyclic polyolefin. The group formed. Examples of the composite material containing a resin include a siloxane resin such as polydimethylsiloxane and polysilsesquioxane; a glass composite substrate; and a glass epoxy substrate. Among these materials, polyester-based resins, polyolefin-based resins, glass composite substrates, and glass epoxy substrates are preferred from the viewpoints of high heat resistance and low linear expansion coefficient. These materials can be used alone or in combination of two or more.

In the laminated body 1 of this embodiment, PEN is used as a forming material of the base material 3.

Although the thickness of the substrate 3 is appropriately set in consideration of stability and the like when manufacturing a laminated film, it is preferably 5 μm to 500 μm in vacuum because the substrate 3 can be easily transported. Furthermore, when the laminated film used in the manufacturing method of this embodiment is formed in the film layer 4, it will be described later. Since the discharge is performed through the substrate 3, the thickness of the substrate 3 is more preferably 50 μm to 200 μm, and particularly preferably 50 μm to 100 μm.

The "thickness of the base material" can be obtained as the average value of the distance from the surface in the thickness direction of the base material at any of nine points.

From the standpoint of adhesion with the formed thin film layer 4, the substrate 3 may be subjected to a surface active treatment to clean the surface thereof. Examples of such a surface-active treatment include a corona treatment, a plasma treatment, and a frame treatment.

(Film layer)

The thin film layer 4 is provided on the surface of the base material 3 (that is, between the base material and the adhesive layer when viewed from the laminate of the product) to ensure gas barrier properties. Although the thin film layer 4 includes at least one layer, it may include a plurality of layers (for example, 2 to 4 layers), and at least each layer includes silicon, oxygen, and hydrogen.

FIG. 2 is a schematic diagram showing the thin film layer 4. The thin film layer 4 shown in the figure includes a first layer 4a containing a large amount of SiO ₂ formed by a complete oxidation reaction of a film-forming gas described later, and a large amount of SiO _x C _y generated by an incomplete oxidation reaction. The second layer 4b, the first layer 4a, and the second layer 4b have a three-layer structure in which layers are alternately laminated. In addition, at least one of the layers constituting the thin film layer 4 may further contain nitrogen, aluminum, and titanium.

However, the diagram schematically shows those distributed in the film composition, in fact, the interface between the first layer 4a and the second layer 4b is not clearly generated, and the composition changes continuously. In the figure, although the thin film layer 4 is shown as a three-layer structure, a plurality of layers may be further laminated. The film layer 4 is composed of more layers than three layers At this time, the first layer 4a is formed at both ends of the lamination direction, and the second layer 4b is configured to be held by the adjacent first layers 4a.

That is, one side of the thin film layer 4 is on the surface of the substrate 3, and the first layer 4a containing a large amount of SiO _{2 and} the second layer 4b containing a large amount of SiO _x C _y generated by incomplete oxidation reaction, A structure in which the first layer 4a containing a large amount of SiO ₂ is laminated in this order.

The other side of the thin film layer 4 is a plurality of first layers 4a containing a large amount of SiO ₂ and a plurality of second layers 4b containing a large amount of SiO _x C _y produced by an incomplete oxidation reaction. The two ends are constituted by the first layer 4a.

(Curl suppression layer)

The curl suppression layer 5 is provided in order to suppress curl (warpage) of the entire laminated film 2. As a material for forming the curl suppressing layer 5, the same material as the film layer 4 described above can be used. The thickness of the curl suppressing layer 5 (hereinafter sometimes referred to as a layer thickness) may be the same as that of the thin film layer 4 described above. The thin film layer 4 and the curl suppression layer 5 are preferably made of the same forming material, the same layer structure, and the same thickness. The thickness of the curl suppression layer 5 can be obtained by the same method as the thickness of the thin film layer 4 described later.

The curl suppression layer 5 may not be formed.

That is, the other side of the laminated body 1 according to this embodiment includes a laminated film 2 and an adhesive layer 6; the laminated film 2 includes a base material 3 and a film layer 4; and the film layer 4 is provided on a base Between the material 3 and the adhesive layer 6.

(Adjacent layer)

The next layer 6 has a function of adhering the laminated body 1 to another member. As a material for forming the adhesive layer 6, conventionally known materials can be used, and for example, a thermosetting resin composition or a photocurable resin composition can be used.

Examples of the thermosetting resin composition include a phenol resin, an epoxy resin, a melamine resin, a urea resin, an unsaturated polyester resin, an alkyd resin, a polyurethane resin, and a thermosetting polyurethane. Examples of the amine include a composition containing a solvent or a viscosity modifier, if necessary. Examples of the photocurable resin composition include an acrylate resin and an epoxy resin, and if necessary, a composition including a solvent or a viscosity modifier.

The adhesive layer 6 is composed of a resin composition having a polymerizable functional group remaining. The resin composition constituting the adhesive layer 6 can be further polymerized by making the laminate 1 and other members adhere to each other, which can be used as a structure for achieving strong adhesion.

In addition, the adhesive layer 6 is made of a thermosetting resin composition or a photocurable resin composition as a material and can be used to polymerize and harden the resin by supplying energy after the fact. It is a pressure sensitive adhesive (Pressure Sensitive Adhesive, PSA).

As a pressure-sensitive adhesive, you can use "adhesives at room temperature and adhere to the substrate with light pressure" (JIS K6800), that is, adhesives, or "the specific component as a protective film (microcapsule)" , Until the membrane is destroyed by appropriate means (pressure, heat, etc.) An adhesive that can maintain stability "(JIS K6800) is a capsule adhesive.

The thickness of the adhesive layer 6 (hereinafter sometimes referred to as a film thickness) may be 100 μm or less. When the thickness of the adhesive layer 6 is less than 10 μm, the impact resistance is expected to decrease or wrinkles are likely to occur. Therefore, the thickness is preferably 10 μm or more. That is, the thickness of the adhesive layer 6 is preferably 10 μm or more and 100 μm or less.

As shown in the figure, the adhesive layer 6 can be composed of one layer, that is, a double-sided tape. Since the adhesive layer is provided on both sides of the film serving as the substrate, the adhesive layer 6 can have a laminated structure capable of adhesive on both sides.

The moisture content of the laminated body 1 suppresses the influence on the object sealed by the laminated body 1, and is preferably 0.1% by mass or less based on the total mass of the laminated body 1. The moisture content of the laminated body 1 can be reduced by, for example, drying under reduced pressure, heat drying, or drying under reduced pressure.

The moisture content of the laminate 1 is approximately 0.1 g of a test piece from the laminate 1 and a fine scale is produced. The test piece can be heated at 150 ° C for 3 minutes in a Karl Fischer moisture meter, and borrowed Calculated from the amount of water produced.

The laminated body 1 manufactured by the manufacturing method of this embodiment has a structure as mentioned above.

[Manufacturing method of laminated body]

3 and 4 are explanatory diagrams showing a method for manufacturing a laminated body according to this embodiment. The method for producing a laminated body according to this embodiment includes forming a substrate A step of forming a thin film layer, and a step of forming an adhesive layer on the formed laminated film; The following description will be described as a case where the curl suppressing layer 5 shown in FIG. 1 is not provided.

(Step of forming a thin film layer)

FIG. 3 is an explanatory diagram showing a step of forming a thin film layer, and is a schematic view of a film forming apparatus 10 that performs the step of forming a thin film layer.

The film forming apparatus 10 shown in the figure includes an unwinding roll 11, a winding roll 12, a conveying roll 13 to 16, a film forming roll 17, 18, a gas supply pipe 19, a plasma generating power source 20, and electrodes 21 and 22 A magnetic field forming device 23 provided inside the film forming roller 17 and a magnetic field forming device 24 provided inside the film forming roller 18. Among the constituent elements of the film forming apparatus 10, at least the film forming rollers 17, 18, the gas supply pipe 19, and the magnetic field forming apparatuses 23 and 24 are arranged in a vacuum chamber (not shown) when manufacturing a laminated film. This vacuum chamber is connected to a vacuum pump (not shown). The pressure inside the vacuum chamber is adjusted by the operation of the vacuum pump.

When using this device, by controlling the plasma generating power source 20, a discharge plasma of the supplied film forming gas can be generated from the gas supply pipe 19 in the space between the film forming roller 17 and the film forming roller 18, and the The generated discharge plasma is formed by plasma CVD.

The unwinding roller 11 is provided in a state of the base fabric 3A before being wound into a film, and the base fabric 3A is unwound to the longitudinal direction and supplied. In addition, a winding roll 12 is provided on an end portion side of the base fabric 3A, and the base fabric 3A after being subjected to film formation is pulled and wound into a roll shape.

The base fabric 3A has a band shape, and is cut to a specific length in each direction that intersects with the longitudinal direction, thereby becoming the base 3 of FIG. 1 described above. As a material for forming the base fabric 3A, the same material as the material for forming the base material 3 described above can be used. In the manufacturing method of the laminated body of this embodiment, PEN is used as the forming material of the base fabric 3A.

The film-forming roller 17 and the film-forming roller 18 extend in parallel and are arranged to face each other. The two rolls are formed of a conductive material, and each of them rotates and transports the base fabric 3A. The film-forming roller 17 and the film-forming roller 18 are insulated from each other and are connected to a common plasma generating power source 20 at the same time. When applied from the plasma generating power source 20, an electric field is formed in the space SP between the film forming roller 17 and the film forming roller 18.

Further, the film forming rollers 17 and 18 are connected to internal magnetic field forming devices 23 and 24. The magnetic field forming devices 23 and 24 are members that form a magnetic field in the space SP, and are stored so that the film forming roller 17 and the film forming roller 18 do not rotate together.

The magnetic field forming devices 23 and 24 include center magnets 23a and 24a extending in the same direction as the extending directions of the film forming rollers 17 and 18, and surrounding the central magnets 23a and 24a, and forming films with the film forming rollers 17, and The ring-shaped external magnets 23b and 24b arranged in the same direction as the roller 18 are extended in the same direction. In the magnetic field forming device 23, an endless tunnel is formed by combining the magnetic field lines (magnetic circles) of the central magnet 23a and the external magnet 23b. Even in the magnetic field forming device 24, the endless tunnel is formed by combining the magnetic field lines of the central magnet 24a and the external magnet 24b.

By this magnetic line of force, and between the film forming roller 17 and the film forming roller 18 The electric field formed between them is the discharge of the crossed magnetrons, which causes the discharge plasma to form a film-forming gas. That is, as described later in detail, the space SP is used as a film forming space for plasma CVD film formation, and is formed on the base fabric 3A on the surface (ie, the film forming surface) that is not in contact with the film forming rollers 17, 18. A film-forming gas is used as a thin-film layer of a forming material.

A gas supply pipe 19 is provided near the space SP to supply a film-forming gas such as a plasma gas CVD source gas. The gas supply pipe 19 has a tubular shape extending in the same direction as the extending direction of the film forming roller 17 and the film forming roller 18, and supplies film forming gas to the space SP from openings provided at a plurality of points. In FIG. 3, the state where the film-forming gas is supplied from the gas supply pipe 19 to the space SP is shown by arrows.

The raw material gas can be appropriately selected and used according to the material of the barrier film formed. As the source gas, for example, an organic silicon compound containing silicon can be used. Examples of such an organosilicon compound include hexamethyldisilazane, 1,1,3,3-tetramethyldisilaxane, vinyltrimethylsilane, methyltrimethylsilane, and hexamethylsiloxane. Disilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxy Silane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, dimethyldisilazane, trimethyldisilazane, tetramethyl Methyldisilazane, pentamethyldisilazane, hexamethyldisilazane, etc. Among these organosilicon compounds, hexamethyldisilazane and 1,1,3,3-tetramethyl are preferred from the viewpoints of the operability of the compound or the gas barrier properties of the obtained barrier film. Disiloxane. Moreover, these organic silicon compounds may One type can be used alone or in combination of two or more types. Furthermore, as the source gas, in addition to the above-mentioned organosilicon compound, a monosilane can also be contained and used as a silicon source for the formed barrier film.

As the film-forming gas, a reaction gas may be used in addition to the source gas. As such a reaction gas, a gas that reacts with a raw material gas and becomes an inorganic compound such as an oxide or nitride can be appropriately selected and used. As a reaction gas for forming an oxide, for example, oxygen and ozone can be used. Examples of the reaction gas for forming a nitride include nitrogen and ammonia. These reaction gases can be used singly or in combination of two or more kinds. For example, when forming an oxynitride, the reaction gas used to form an oxide can be used in combination with the reaction gas used to form a nitride.

As the film-forming gas, a carrier gas may be used if necessary to supply a source gas into the vacuum chamber. Furthermore, in order to generate a discharge plasma as a film-forming gas, a discharge gas can be used if necessary. As such a carrier gas and a discharge gas, a well-known gas can be suitably used, for example, a rare gas such as helium (He), argon, neon, xenon, or hydrogen can be used.

Although the pressure (vacuum degree) in the vacuum chamber can be appropriately adjusted according to the type of the raw material gas, etc., the pressure of the space SP is preferably 0.1 Pa to 50 Pa. For the purpose of suppressing the gas-phase reaction, when plasma CVD is determined as a low-pressure plasma CVD method, it is usually 0.1 Pa to 10 Pa. In addition, although the electric power of the electrode drum of the plasma generating device can be appropriately adjusted according to the type of the raw material gas or the pressure in the vacuum chamber, it is preferably 0.1 kW to 10 kW.

Although the transport speed (linear speed) of the base fabric 3A can be adjusted The type of the source gas or the pressure in the vacuum chamber is appropriately adjusted, but it is preferably 0.1 m / min to 100 m / min, and more preferably 0.5 m / min to 20 m / min. When the linear velocity is less than the lower limit value, the base fabric 3A tends to become wrinkled due to heat, and when the linear velocity exceeds the upper limit value, the thickness of the formed barrier film tends to be thin. . That is, when the linear velocity is equal to or higher than the lower limit value, generation of wrinkles due to heat in the base fabric 3A can be suppressed, and when the linear velocity is equal to or lower than the upper limit value, the thickness of the formed barrier film becomes sufficient.

In the film forming apparatus 10 as described above, a film is formed on the base fabric 3A as follows.

First, prior to film formation, prior treatment can be performed in such a manner that the exhaust gas generated from the base fabric 3A becomes very small. The amount of exhaust gas generated from the base fabric 3A can be determined by using the pressure in the decompression device (inside the cavity) when the base fabric 3A is installed in a manufacturing apparatus. For example, if the pressure in the cavity of the manufacturing apparatus is 1 × 10 ^-3 Pa or less, it can be judged that the amount of exhaust gas generated from the base fabric 3A becomes very small.

Examples of the method for reducing the amount of exhaust gas from the base fabric 3A include vacuum drying, heat drying, drying by a combination thereof, and drying by natural drying. Even if it is any drying method, in order to promote the drying of the inside of the base fabric 3A wound into a roll shape, it is preferable to repeat the roll replacement (unwinding and winding) of the roll during drying, and 3A was exposed to a dry environment.

The vacuum drying is performed by putting a vacuum container having a pressure resistance into the original base fabric 3A, and using a pressure reducer such as a vacuum pump to exhaust the inside of the vacuum container to obtain a vacuum. The pressure in the vacuum container during vacuum drying is preferably 1 × 10 ^-6 Pa or more and 1000 Pa or less, more preferably 1 × 10 ^-5 Pa or more and 100 Pa or less, and even more preferably 1 × 10 ^-4 Pa or more, 10Pa or less. The exhaust in the vacuum container can be performed continuously by continuously operating the pressure reducer, and the internal pressure can be managed in such a way that it cannot be more than a certain value, and can be intermittently performed by intermittently operating the pressure reducer. The drying time is preferably at least 8 hours, more preferably 1 week or more, and even more preferably 1 month or more.

The heating and drying are performed by exposing the base fabric 3A to an environment of 50 ° C or higher. The heating temperature is preferably 50 ° C or higher and 200 ° C or lower, and more preferably 70 ° C or higher and 150 ° C or lower. When the temperature exceeds 200 ° C, the base fabric 3A may be deformed. In addition, the oligomer component is eluted from the base fabric 3A and deposited on the surface, which may cause defects. The drying time can be appropriately selected depending on the heating means used for the heating temperature.

The heating means is not particularly limited as long as it can heat the base fabric 3A from 50 ° C. to 200 ° C. under normal pressure. Among commonly known devices, an infrared heating device, a microwave heating device, and a heating drum are preferably used.

Here, the so-called "infrared heating device" is a device that heats an object by emitting infrared rays from an infrared generation means.

The so-called "microwave heating device" is a device that irradiates microwaves by means of microwave generation to heat an object.

The so-called "heating roller" is a device that heats the surface of the roller to bring the object into contact with the surface of the roller, and heats it from the contact part by heat conduction.

Natural drying is to arrange the base fabric 3A in a low humidity atmosphere It is performed by ventilating a dry gas (dry air or dry nitrogen) to maintain a low-humidity atmosphere. When natural drying is performed, it is preferable to arrange a desiccant such as silica gel together in a low-humidity environment with a base fabric of 3A. The drying time is preferably at least 8 hours, more preferably 1 week or more, and even more preferably 1 month or more.

Such drying may be performed in other ways before the base fabric 3A is installed in the manufacturing apparatus, or after the base fabric 3A is installed in the manufacturing apparatus, the drying may be performed in the manufacturing apparatus.

Examples of a method of mounting the base fabric 3A on the manufacturing apparatus and drying the base fabric include a method of unwinding and transporting the base fabric 3A from an unwinding roll and decompressing the inside of the chamber. Further, the passing roller is a roller having a heater, and the heating roller can be used as the above-mentioned heating roller for heating.

As another method for reducing the exhaust gas from the base fabric 3A, an inorganic film may be formed on the surface of the base fabric 3A in advance. Examples of the film formation method of the inorganic film include physical film formation methods such as vacuum vapor deposition (heat vapor deposition), electron beam (Electron Beam, EB) vapor deposition, sputtering, and ion plating. In addition, an inorganic film can be formed by a chemical deposition method such as thermal CVD, plasma CVD, or atmospheric pressure CVD. Furthermore, by performing a drying treatment on the surface of the base fabric 3A for forming an inorganic film by the above-mentioned drying method, the influence of exhaust can be further reduced.

That is, one side of the manufacturing method of the present invention may be included in the vacuum drying, heating drying, and vacuum drying so that the amount of exhaust gas generated from the base fabric 3A becomes very small before forming the film layer. Drying in combination with heat drying, and natural drying; or may include An inorganic film is formed on the surface of the base fabric 3A.

Next, the vacuum chamber (not shown) is used as a decompression environment, and the film forming roller 17 and the film forming roller 18 are applied to generate an electric field in the space SP.

At this time, in order to form the above-mentioned endless tunnel-like magnetic field in the magnetic field forming devices 23 and 24, a film-forming gas is introduced, and electrons released from the magnetic field and space SP are used to form the tunnel along the aforementioned tunnel. The discharge plasma of a donut-like film-forming gas. This discharge plasma can be generated at a low pressure around a few Pa, so the temperature in the vacuum chamber can be near room temperature.

In addition, since the temperature of the electrons captured at a high density in the magnetic field forming devices 23 and 24 is high, a discharge plasma is generated due to the collision between the electrons and the film-forming gas. That is, by the magnetic field and electric field formed by the space SP, electrons are enclosed in the space SP, and a high-density discharge plasma is formed in the space SP. More specifically, a high-density (high-intensity) discharge plasma is formed in a space overlapping with an endless tunnel-like magnetic field, and a low-density (- Low-intensity) discharge plasma. The strength of these discharge plasmas changes continuously.

When a discharge plasma is generated, a large amount of radicals or ions are generated to perform a plasma reaction, and a reaction between a raw material gas and a reaction gas contained in the film-forming gas is generated. For example, an organic silicon compound, which is a raw material gas, reacts with oxygen, which is a reactive gas, to produce an oxidation reaction of the organic silicon compound.

Here, in the space where a high-strength discharge plasma is formed, the reaction is easy to proceed due to the large amount of energy given by the oxidation reaction, and can be produced as the main Complete oxidation of organosilicon compounds. In addition, in the space where a low-strength discharge plasma is formed, the reaction is difficult to proceed due to the small amount of energy given by the oxidation reaction, and an incomplete oxidation reaction as a main organosilicon compound may occur.

In the present specification, the "complete oxidation reaction of an organosilicon compound" means that a reaction between the organosilicon compound and oxygen is carried out to completely oxidize and decompose the organosilicon compound into silicon dioxide (SiO ₂ ), water, and carbon dioxide. "Partial oxidation reaction of the organic silicon compound" so-called, refers to an organic silicon compound oxidation reaction is not complete, but becomes not produce SiO ₂ SiO _x C _y containing carbon in the structure (0 <x <2,0 <y <2).

As mentioned above, since the discharge plasma is formed into a doughnut shape on the surfaces of the film forming rollers 17 and 18, the original base fabric 3A transported to the surfaces of the film forming rollers 17 and 18 becomes alternately formed. Space for high-intensity discharge plasma and space for low-intensity discharge plasma. Therefore, on the surface of the base fabric 3A passing through the surfaces of the film forming rollers 17 and 18, SiO ₂ generated by the complete oxidation reaction and SiO _x C _y generated by the incomplete oxidation reaction are alternately formed. .

In addition to this, high-temperature secondary electrons prevent the base fabric 3A from flowing into the base fabric by the action of a magnetic field. Therefore, it becomes possible to suppress the base fabric 3A at a low temperature and directly input high power to achieve high-speed film formation. The film deposition mainly occurs only on the film-forming surface of the base fabric 3A. Since the film-forming roller is coated on the base fabric 3A, it is not easy to be contaminated, and it can form a stable film for a long time.

The thin film layer 4 formed in this way is a thin film layer 4 containing silicon, oxygen, and carbon. The ratio of the surface distance of silicon to the amount of silicon atoms relative to the total amount of silicon atoms, oxygen atoms, and carbon atoms (hereinafter, sometimes referred to as the atomic ratio of silicon), and the ratio of the amount of oxygen atoms (hereinafter, The silicon distribution curve, oxygen distribution curve, and carbon distribution curve that are related to the ratio of the number of atoms of oxygen) and the ratio of the number of carbon atoms (hereinafter, also sometimes referred to as the number of atoms of carbon) satisfy the following Conditions (i) to (iii) are all.

(i) First, the thin film layer 4 is such that the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more and 100% or less (more preferably 95% or more and 100% or less) of the film thickness of the aforementioned layer. In the following, a particularly preferred region is 100%), which satisfies the condition represented by the following formula (1), (atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon) (1).

When the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon of the thin film layer 4 satisfy the condition (i), the gas barrier property of the obtained gas barrier laminated film becomes sufficient.

(ii) Further, the carbon distribution curve of the thin film layer 4 system has at least one extreme value.

In the thin film layer 4, it is more preferable that the carbon distribution curve has at least two extreme values, and particularly preferably has at least three extreme values. When the carbon distribution curve does not have an extreme value, the gas barrier properties are insufficient when the film of the obtained gas barrier laminated film is bent. In addition, when there are at least three extreme values, one extreme value of the carbon distribution curve and the thickness direction of the thin film layer 4 from the extreme value adjacent to the extreme value to the thin film layer 4 The absolute value of the difference in distance between the surfaces is preferably less than 200 nm, and more It is preferably 100 nm or less.

In the present embodiment, the "extreme value" means the maximum value or minimum value of the atomic number ratio of the element in the thin film layer 4 with respect to the distance from the film thickness direction of the thin film layer 4 to the surface of the thin film layer 4. . The “maximum value” in the present specification refers to a case where the distance from the thin film layer 4 to the surface of the thin film layer 4 is changed, and the value of the atomic ratio of the element is changed from an increase to a decrease. The value of the atomic ratio of the element at this point is further changed from the aforementioned point to the distance from the film thickness direction of the thin film layer 4 to the surface of the thin film layer 4 by the atomic ratio (atomic composition) of the element at the position of 20 nm. (Percentage) value, more than 3at% points. Furthermore, the "minimum value" in this embodiment refers to a case where the distance from the surface of the thin film layer 4 is changed in the thin film layer 4, and the value of the atomic ratio of the element changes from a decrease to an increase, and the phase The value of the atomic ratio of the element at this point is further changed from the aforementioned point to the distance from the film thickness direction of the thin film layer 4 to the surface of the thin film layer 4 by the atomic ratio of the element at the 20 nm position (atoms The composition percentage) value is increased by more than 3at%.

(iii) Further, the absolute value of the difference between the maximum value and the minimum value of the carbon atom number ratio of the carbon layer in the carbon distribution curve of the thin film layer 4 is 5 at% or more.

In the thin film layer 4, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon is more preferably 6at% or more, and particularly preferably 7at% or more. When the absolute value is less than 5 at%, the gas barrier properties in the case where the film of the obtained gas barrier laminate film is bent are insufficient. That is, the absolute value When it is 5 at% or more, the gas barrier properties when the film of the obtained gas barrier laminate film is bent are sufficient.

In this embodiment, the oxygen distribution curve of the thin film layer 4 preferably has at least one extreme value, more preferably has at least two extreme values, and particularly preferably has at least three extreme values. When the oxygen distribution curve does not have an extreme value, the gas barrier property tends to decrease when the film of the obtained gas barrier laminated film is bent. In this case, when there are at least three extreme values, an extreme value adjacent to the oxygen distribution curve and an extreme value adjacent to the aforementioned extreme value are from the thickness direction of the thin film layer 4 to the The absolute value of the difference in surface distance is preferably 200 nm or less, and more preferably 100 nm or less.

In this embodiment, the absolute value of the difference between the maximum value and the minimum value of the oxygen atomic ratio in the oxygen distribution curve of the thin film layer 4 is preferably 5 at% or more, more preferably 6 at% or more, and particularly preferably 7at% or more. When the absolute value is less than the lower limit, the gas barrier property tends to decrease when the film of the obtained gas barrier laminate film is bent. That is, if the absolute value is greater than or equal to the lower limit value, it is possible to suppress a decrease in the gas barrier property when the film of the obtained gas barrier laminated film is bent.

In this embodiment, the absolute value of the difference between the maximum value and the minimum value of the silicon atomic ratio of the silicon distribution curve in the thin film layer 4 is preferably less than 5 at%, more preferably less than 4 at%, and particularly preferably Less than 3at%. When the absolute value exceeds the upper limit, the gas barrier property of the obtained gas barrier laminated film tends to decrease. That is, if the absolute value is equal to or less than the upper limit value, it is possible to suppress a decrease in the gas barrier property of the obtained gas barrier laminate film.

In this embodiment, the thin film layer 4 indicates the distance from the film thickness direction in the thin film layer 4 to the surface of the layer, and the total amount of oxygen atoms and carbon relative to the silicon atom, oxygen atom, and carbon atom. The absolute value of the difference between the maximum value and the minimum value of the oxygen-carbon distribution curve in the relationship of the total atomic ratio (the ratio of the number of oxygen and carbon atoms), It is preferably less than 5 at%, more preferably less than 4 at%, and particularly preferably less than 3 at%. When the absolute value exceeds the upper limit, the gas barrier property of the obtained gas barrier laminated film tends to decrease. That is, if the absolute value is equal to or less than the upper limit value, it is possible to suppress a decrease in the gas barrier property of the obtained gas barrier laminate film.

Here, the silicon distribution curve, oxygen distribution curve, carbon distribution curve, and oxygen-carbon distribution curve are measured by X-ray photoelectron spectroscopy (XPS: Xray Photoelectron Spectroscopy) in combination with argon and other rare gas ion sputtering to make the sample The inside is exposed, and the surface composition analysis is performed sequentially, that is, it can be created by XPS depth analysis measurement. The distribution curve obtained by such XPS depth analysis and measurement can be prepared by using, for example, the vertical axis as the atomic ratio of each element (unit: at%) and the horizontal axis as the etching time (sputtering time). In this case, the distribution curve of the element with the etch time on the horizontal axis is roughly related to the distance from the film thickness direction to the surface of the thin film layer 4. Therefore, it is regarded as "the film thickness from the thin film layer 4". The distance from the direction to the surface of the thin film layer 4 "is the distance of the surface of the thin film layer 4 calculated from the relationship between the etching rate and the etching time used in the XPS depth profile measurement. In addition, as the sputtering method used in the XPS depth profiling measurement, a dilute gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species is preferably used, and the etching rate (etching rate) thereof is set to 0.05. nm / sec (equivalent to SiO ₂ thermal oxide film).

In addition, in this embodiment, from the viewpoint of forming a thin film layer 4 having uniform and excellent gas barrier properties over the entire film surface, it is preferable that the thin film layer 4 is in the film surface direction (that is, parallel to the surface of the thin film layer 4). Direction) is essentially the same. In this specification, "the film layer 4 is substantially the same in the direction of the film surface" means that the oxygen distribution curve and the carbon distribution curve are formed for any two measurement points of the film surface of the film layer 4 by XPS depth analysis and measurement. In the case of oxygen and carbon distribution curves, at any two measurement points, the obtained carbon distribution curve has the same number of extreme values, and the difference between the maximum and minimum values of the carbon atomic ratio of the individual carbon distribution curves. The absolute values are the same as each other or within 5at%.

Furthermore, in this embodiment, it is preferable that the carbon distribution curve is substantially continuous.

In this specification, the "carbon distribution curve is substantially continuous" means that the atomic ratio of carbon in the carbon distribution curve does not include discontinuous changes. Specifically, it refers to the calculation from the etching rate and etching time. The relationship between the distance (x, unit: nm) from the film thickness direction of the thin film layer 4 to the surface of the aforementioned layer, and the atomic ratio (C, unit: at%) of carbon satisfies the following formula (F1): ｜ dC / dx ｜ ≦ 0.01… (F1)

Conditions of representation.

In addition, "dC" means that calculated from the etching rate and etching time The "dx" ratio of the number of carbon atoms in the film thickness direction of the thin film layer 4 to the surface of the aforementioned layer represents the distance from the film thickness direction of the thin film layer 4 to the surface of the aforementioned layer, calculated from the etching rate and etching time.

The gas-barrier laminated film manufactured by the method of this embodiment includes at least one thin film layer 4 that satisfies the above conditions (i) to (iii), but may include two or more layers that satisfy such conditions. Furthermore, when two or more such thin film layers 4 are provided, the material of the plural thin film layers 4 may be the same or different. When two or more such thin film layers 4 are provided, such a thin film layer 4 may be formed on the surface on one side of the substrate, or may be formed on both surfaces of the substrate. The plurality of thin film layers 4 may include a thin film layer 4 which does not necessarily have gas barrier properties.

In addition, in the silicon distribution curve, oxygen distribution curve, and carbon distribution curve, the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are in a region of 90% or more of the film thickness of the aforementioned layer, and satisfy the formula (1) In the case of the conditions indicated, the atomic ratio of the content of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the thin film layer 4 is preferably 25 at% or more and 45 at% or less, and more preferably Above 30at% and below 40at%. In addition, the atomic ratio of the content of oxygen atoms is preferably 33at% or more and 67at% or less, more preferably 45at% or more and 67at% or more relative to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the thin film layer 4. the following. Furthermore, the atomic ratio of the content of carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the thin film layer 4 is preferably 3 at% or more and 33 at% or less, and more preferably 3 at% or more and 25 at%. %the following.

Furthermore, in the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve, the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are in a region of 90% or more of the film thickness of the aforementioned layer, and satisfy the formula (2) In the case of the conditions indicated, the atomic ratio of the content of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the thin film layer 4 is preferably 25 at% or more and 45 at% or less, and more preferably Above 30at% and below 40at%. The atomic ratio of the content of oxygen atoms is preferably 1 at% or more and 33 at% or less, and more preferably 10 at% or more and 27 at% or more relative to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the thin film layer 4. the following. Furthermore, the atomic ratio of the content of carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the thin film layer 4 is preferably 33 at% or more and 66 at% or less, and more preferably 40 at% or more and 57 at%. %the following.

The thickness (also referred to as the film thickness) of the thin film layer 4 is preferably in a range of 5 nm or more and 3000 nm or less, more preferably in a range of 10 nm or more and 2000 nm or less, and particularly preferably in a range of 100 nm or more and 1000 nm or less. When the thickness of the thin film layer 4 is less than the lower limit, the gas barrier properties such as aerobic gas barrier properties and water vapor barrier properties tend to deteriorate. When the thickness exceeds the upper limit, the gas barrier properties tend to be lowered due to bending. That is, when the thickness of the thin film layer 4 is greater than or equal to the lower limit value, gas barrier properties such as oxygen gas barrier property and water vapor barrier property are good. When the thickness is less than or equal to the upper limit value, it is difficult to reduce the gas barrier property due to bending.

In addition, in the case where the gas barrier laminated film of this embodiment includes a plurality of thin film layers 4, the total value of the thickness (film thickness) of such thin film layers 4 is usually in a range of 10 nm or more and 10,000 nm or less, preferably The range is from 10 nm to 5000 nm, more preferably from 100 nm to 3000 nm, and particularly preferably from 200 nm to 2000 nm. When the total value of the thickness of the thin film layer 4 is less than the lower limit value, the gas barrier properties such as aerobic gas barrier property and water vapor barrier property tend to deteriorate. When the total value exceeds the upper limit, the gas barrier property is liable to decrease due to bending. tendency. That is, when the total value of the thickness of the thin film layer 4 is greater than or equal to the lower limit value, gas barrier properties such as oxygen gas barrier property and water vapor barrier property are good, and when it is less than or equal to the upper limit value, it is difficult to reduce gas barrier properties due to bending.

In order to form such a thin film layer 4, as a ratio of the source gas and the reaction gas contained in the film-forming gas, in order to completely react the source gas and the reaction gas, it is preferably a ratio of the amount of the reaction gas that is theoretically necessary, Nor should the ratio of excess reaction gas be excessive. When the ratio of the reaction gas becomes excessive, the thin film layer 4 that satisfies all of the conditions (i) to (iii) described above cannot be obtained.

Hereinafter, a film-forming gas containing hexamethyldisilazane (HMDSO: (CH ₃ ) ₆ Si ₂ O :) as a raw material gas and oxygen (O ₂ ) as a reaction gas will be used to produce a silicon-oxygen-based The case of the thin film layer is taken as an example, and a suitable ratio of the source gas and the reaction gas in the film-forming gas will be described in more detail.

When a film-forming gas containing HMDSO as a raw material gas and oxygen as a reaction gas is reacted by plasma CVD to form a silicon-oxygen thin film layer, the following reaction formula is caused by the film-forming gas ( 1) The reaction described above produces silicon dioxide.

[Formula _{1] (CH 3) 6 Si} 2 O + 12O 2 → 6CO 2 + 9H 2 O + 2SiO 2 ... (1)

In such a reaction, the amount of oxygen necessary to completely oxidize HMDSO1 mole is 12 moles. Therefore, in the film-forming gas, since it contains 12 mol or more of oxygen relative to 1 mol of HMDSO, when a complete reaction is used, a uniform silicon dioxide film is formed, and it is impossible to form a film that satisfies the above condition (i). ~ (iii) 的 inspection4. Therefore, when the thin film layer 4 of this embodiment is formed, the amount of oxygen must be reduced to less than the stoichiometric amount of 12 moles relative to 1 mole of HMDSO so that the reaction of the above formula (1) cannot be performed.

However, the reaction in the vacuum chamber of the film forming apparatus 10, the HMDSO of the raw material and the oxygen of the reaction gas are formed by supplying the film formation area from the gas supply unit, and the molar amount (flow rate) of the oxygen of the reaction gas is even It is 12 times the molar amount (flow rate) of the HMDSO (flow rate) of the raw material. In reality, the reaction cannot be completely performed. Comparing the oxygen content with the stoichiometric ratio, it is considered to be a large excess supply. The reaction is completed for the first time. (For example, in order to obtain silicon oxide which is completely oxidized by CVD, the molar amount (flow rate) of oxygen may be about 20 times or more the molar amount (flow rate) of HMDSO of the raw material). Therefore, the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of HMDSO of the raw material is preferably a stoichiometric ratio, that is, an amount that is 12 times or less (more preferably 10 times or less).

By containing HMDSO and oxygen at such a ratio, carbon atoms or hydrogen atoms in the incompletely oxidized HMDSO are injected into the thin film layer 4 to form a thin film that satisfies all of the above conditions (i) to (iii). The layer 4 becomes an excellent barrier property and bending resistance of the obtained gas-barrier laminated film.

However, when the molar amount (flow rate) of oxygen relative to the molar amount (flow rate) of HMDSO in the film-forming gas is too small, this situation is reduced due to excessive intake of unoxidized carbon atoms or hydrogen atoms in the thin film layer 4. Transparency of the barrier film. Such a gas barrier film makes it impossible to use a flexible substrate for a device in which transparency such as an organic EL device or an organic thin film solar cell is required. From such a point of view, it is preferable that the lower limit of the molar amount (flow rate) of oxygen relative to the molar amount (flow rate) of HMDSO in the film-forming gas is more 0.1 of the molar amount (flow rate) of HMDSO The amount is more preferably 0.5 times more.

That is, the molar amount (flow rate) of oxygen relative to the molar amount (flow rate) of HMDSO in the film-forming gas is preferably 0.1 times or more and 12 times the molar amount (flow rate) of HMDSO or more. It is preferably 0.5 times or more and 10 times or less.

In this way, whether or not the organic silicon compound is completely oxidized can be controlled by applying a voltage to the film forming roller 17 and the film forming roller 18 in addition to the mixing ratio of the raw material gas and the reaction gas in the film forming gas.

By the plasma CVD method using such a discharge plasma, the continuous film layer 4 can be formed on the surface of the base fabric 3A wound around the film forming rollers 17 and 18.

When the curl suppression layer 5 is formed, after the film layer 4 is formed, a film is formed on a surface on the side opposite to the surface on which the film layer 4 of the base fabric 3A is formed. The curl suppressing layer 5 can be used under the same conditions as those for forming the thin film layer 4 The film is formed under the conditions, and can have the same composition, the same layer structure, and the same layer thickness (thickness) as those of the thin film layer 4. Of course, by changing the formation conditions of the curl suppression layer 5 and the formation conditions of the thin film layer 4, the composition, layer structure, and layer thickness of the curl suppression layer 5 may be different from those of the thin film layer 4.

That is, one side of the method for manufacturing a laminated body of the present invention includes a step of forming an adhesive layer, a step of forming a thin film layer, and a step of further forming a curl suppressing layer as desired; The same conditions as those of the step of forming the thin film layer may be performed, and they may be performed under different conditions.

Thereby, the laminated film can be manufactured as a continuous laminated film original fabric 2A in a strip shape. The laminated film original fabric 2A becomes a laminated film 2 by being cut to a specific length in each direction intersecting with the longitudinal direction.

(Step of Forming Adhesive Layer)

FIG. 4 is an explanatory diagram showing a step of forming an adhesive layer, and is a schematic diagram of a manufacturing apparatus 100 that performs the step of forming an adhesive layer.

The manufacturing apparatus 100 shown in the drawing includes a first unwinding roll 110, a winding roll 120, a second unwinding roll 130, a bonding roll 140, and a surface treatment device 150.

In the first unwinding roll 110, the film layer is placed facing outward and the laminated film original fabric 2A is wound. The laminated film original fabric 2A is unwound in the longitudinal direction and supplied.

The winding roll 120 is provided on the end side of the laminated film original cloth 2A, and is pulled to form the laminated film original cloth 2A (the lamination described later) The original fabric 1A) is rolled and stored in a roll shape.

The second unwinding roller 130 is provided in a state where the adhesive film 8A is wound in a belt shape, and the adhesive film 8A is unwound in the longitudinal direction and supplied. Next, the film 8A is attached to one side of the strip-shaped separation film 7A, and if the adhesive layer 6A is provided in a belt shape, the adhesive layer 6A is wound onto the second unwinding roller 130 with the outer side facing.

The bonding layer 6A corresponds to the "bonding layer original cloth" in the present invention. As a material for forming the adhesive layer 6A, the same material as the material for forming the adhesive layer 6 described above can be used.

The release film 7A is releasably attached to one surface of the adhesive layer 6A. When the release film 7A is peeled from the adhesive film 8A, the adhesive layer 6A is exposed and becomes adhesive.

The bonding roller 140 includes a pair of rollers 141 and 142. The laminating roll 140 penetrates the laminated film original cloth 2A and the adhesive film 8A from the same direction with respect to the gap between the pair of rollers. The two are pressed together to form a laminated raw fabric 1A. Specifically, the laminating roll 140 is formed by laminating both the film layer of the film original fabric 2A and the adhesive layer 6A of the film 8A facing each other to form a layered original fabric 1A. The laminated original fabric 1A is cut into a specific length in each direction intersecting with the longitudinal direction, thereby becoming the laminated object 1 which is the object of the method for manufacturing a laminated body according to this embodiment.

In the manufacturing method of the laminated body of this embodiment, with respect to the laminated film original cloth 2A, a tension of 0.5N / mm ² or more and less than 50N / mm ² per unit cross-sectional area is added in the longitudinal direction, and the paste is applied. The laminated film original fabric 2A and the adhesive film 8A are laminated, and an adhesive layer is formed on one side of the laminated film original fabric 2A. In the manufacturing apparatus 100, the tension of the laminated film original fabric 2A between the first unwinding roll 110 and the bonding roll 140 falls within the above range.

In this specification, the cross-sectional area in the "unit cross-sectional area" means a cross-section when cut with a plane perpendicular to the longitudinal direction.

That is, one side of the manufacturing method of the laminated body of this embodiment is in the longitudinal direction with respect to the laminated film original cloth 2A in the longitudinal direction, and the unit cross-sectional area is 0.5N / mm ² or more and less than 50N. In a state of tension of / mm ² , the laminated film original fabric 2A and the adhesive film 8A are laminated, and an adhesive layer is formed on one side of the laminated film original fabric 2A.

By adding the above-mentioned tension to the laminated film original fabric 2A, even if the laminated film original fabric 2A is wound into a roll shape by being wound on the first unwinding roll 110, the laminated film original fabric 2A can be bonded well to the adhesive film 8A, and appearance defects are not easy to occur. .

In addition, when the tension added to the laminated film original fabric 2A is 0.5 N / mm ² or more, it is difficult to form wrinkles in the laminated original fabric 1A, and it is difficult to cause appearance defects. In addition, when the tension added to the laminated film original cloth 2A is less than 50 N / mm ² , it is difficult to destroy the film layer even if the laminated body 1 is added, and it is easy to maintain the gas barrier property.

In addition, in the manufacturing method of the laminated body of this embodiment, it is preferable to add a tension per unit cross-sectional area of 0.01 N / mm ² or more and less than 5 N / mm ² to the adhesive film 8A in the longitudinal direction. Then, the laminated film original fabric 2A and the adhesive film 8A are laminated, and an adhesive layer is formed on a surface on one side of the laminated film original fabric 2A. The added tension is more preferably if the cross-sectional area per unit is 0.1 N / mm ² or more and less than 0.5 N / mm ² . In the manufacturing apparatus 100, the tension of the film 8A between the second unwinding roll 130 and the bonding roll 140 is in the above range.

That is, one side of the manufacturing method of the laminated body of the present embodiment, with respect to the adhesive film 8A, includes in the longitudinal direction by adding per unit cross-sectional area of 0.01 N / mm ² or more and less than 5 N / mm ² . In a state of tension, the laminated film original fabric 2A and the adhesive film 8A are bonded together, and an adhesion layer is formed on one side of the laminated film original fabric 2A.

When the tension added to the film 8A is 0.01 N / mm ² or more, it is difficult to form wrinkles on the laminate original fabric 1A, and it is difficult to cause appearance defects. In addition, when the tension added to the laminated film original cloth 8A is less than 5 N / mm ² , then the film 8A is stretched to reduce the risk of deformation, and it is easy to manufacture the laminated body 1 as designed.

The tension added to the laminated film original fabric 2A can be adjusted by adjusting the unwinding speed (rotation speed) of the first unwinding roller 110 and the rotation speed of the bonding roller 140. The tension applied to the film 8A can be adjusted by adjusting the unwinding speed (rotation speed) of the second unwinding roller 130 and the rotation speed of the bonding roller 140. When the rotation speed of the laminating roll 140 is adjusted, it affects both the tension added to the laminated film original cloth 2A and the tension added to the subsequent film 8A. In the case of adjusting the tension individually, the first unwinding roll 110 is adjusted. Or, the rotation speed of the second unwinding roller 130 is better.

The laminating roller 140 can be a roller 141 having a heating pair, Composition of 142. The laminating roller 140 having such a structure can heat and laminate the original film cloth 2A and the adhesive film 8A by heating and laminating the original film cloth 2A and the adhesive film 8A, so that the two can oppose each other. The contact area of the surface (laminating surface) is increased, and the effect of improving adhesion is expected. When the material for forming the adhesive layer 6A is a thermosetting resin, curing is promoted.

The heating temperature may be a temperature exceeding the glass transition temperature (Tg) of at least one of the resin constituting the laminated film original fabric 2A and the resin constituting the adhesive film 8A. At such a temperature, the laminated film original fabric 2A or the adhesive film 8A can be thermally deformed, and the above-mentioned effect of improving the adhesion can be expected.

The pressure at the time of bonding is preferably controlled to be, for example, 0.1 MPa or more and 0.5 MPa or less.

The surface treatment device 150 is arranged on the conveyance path of the laminated film original fabric 2A between the first unwinding roll 110 and the bonding roll 140. The surface treatment device 150 is disposed at a position where the surface of the film layer that can face the film 8A facing the film 8A on the laminated original film 2A can be treated. The surface treatment device 150 performs a plasma treatment, a UV ozone treatment, a corona treatment, and the like on the surface of the thin film layer. Thereby, since impurities are removed on the surface of the film layer, and the polar groups such as hydroxyl groups are increased, the adhesion of the laminated film original cloth 2A and the adhesive film 8A can be improved (the peel strength is improved).

In addition, the manufacturing apparatus 100 can have a well-known structure, such as a winding roll provided with the protective film which winds the adhesive film 8A, or a conveyance roll used when conveying each film.

From the laminated original fabric 1A manufactured as described above, for example, by unwinding from the winding roll 120 and cutting each of them to a specific length in a direction intersecting with the longitudinal direction, the adhesive layer 6 is separated from the adhesive layer 6膜 的 层 体 1。 Thin film laminate 1.

That is, the method for manufacturing a laminated body of the present invention may include, as one side surface, cutting the original laminated cloth 1A formed by the aforementioned manufacturing steps further in a direction intersecting with a longitudinal direction.

Furthermore, the aforementioned method may include peeling the separation film.

The manufacturing method of the laminated body of this embodiment is comprised as mentioned above.

According to the manufacturing method of the laminated body comprised as mentioned above, the manufacturing method of the laminated body which can suppress the damage of the thin film layer which has gas-barrier property, or generation | occurrence | production of an appearance defect can be provided.

[Second Embodiment]

Fig. 5 is an explanatory diagram of a method for manufacturing a laminated body according to a second embodiment of the present invention. The manufacturing method of the laminated body of this embodiment is partly the same as the manufacturing method of the laminated body of the first embodiment, and the steps for forming an adhesive layer are different. Accordingly, in this embodiment, the same reference numerals are given to the constituent elements that are common to the first embodiment, and detailed description is omitted.

(Step of Forming Adhesive Layer)

FIG. 5 is an explanatory diagram showing a step of forming a bonding layer in this embodiment, and is a schematic diagram of a manufacturing apparatus 200 that performs a step of forming a bonding layer.

The manufacturing apparatus 200 shown in the figure is equipped with a first unwinding roller 110, a winding roll 120, a surface treatment device 150, a coating device 160, and a hardening device 170.

The coating device 160 is arranged on the conveyance path of the laminated film original fabric 2A between the surface treatment device 150 and the winding roll 120. The coating device 160 is a composition for coating a precursor of a liquid adhesive layer on the surface of the film layer opposite to the laminated film original cloth 2A and the adhesive film 8A.

The coating device is provided with a tank (not shown) for storing the composition of the precursor, a coating part of the composition of the precursor facing the discharged and laminated film original cloth 2A, and a connection tank and coating. The pump is not shown. In FIG. 5, only the application part with the reference number 160 is shown.

As the coating section, a conventionally known structure capable of coating a liquid precursor can be used. For example, a dispenser, a die coater, a rod coater, a slit coater, and a spray coat can be used. Cloth device or printing press.

The composition of the aforementioned precursor may be a curable resin, a photopolymerization initiator, a composition (a photocurable composition) containing a solvent or a viscosity modifier if necessary, etc., and may be a substitute for the photopolymerization initiator. A composition (thermosetting composition) containing a thermal decomposition type polymerization initiator. In this embodiment, a photocurable composition is used.

By adjusting the coating amount of the aforementioned composition of the precursor from the coating device 160 and the conveying speed of the laminated film original fabric 2A by the first unwinding roll 110 and the winding roll 120, the laminated film original can be adjusted. The thickness (film thickness) of the coating film 60 of the precursor composition formed on the surface of the cloth 2A.

The hardening device 170 is provided with a machine for promoting hardening of the coating film 60 can. In this embodiment, since the composition as a precursor is changed to use a photocurable composition, as the curing device 170, for example, a light source that can irradiate light such as ultraviolet rays is used. In the curing device 170, the coating film 60 is irradiated with ultraviolet rays, and the coating film 60 irradiated with ultraviolet rays is hardened by a photopolymerization reaction to accelerate the polymerization reaction to form an adhesive layer 6A. In the case where the composition of the precursor of the coating and coating device 160 is a thermosetting composition, as the curing device 170, a heat source such as an infrared irradiation device or a heater is used.

In the manufacturing method of the laminated body in this embodiment, the tension in the longitudinal direction with respect to the laminated film original cloth 2A includes a tension of 0.5N / mm ² or more and less than 50N / mm ² per unit cross-sectional area. In this state, the coating film 60 is formed on the surface of the laminated film original fabric 2A, and the adhesion layer is formed on the side of the laminated film original fabric 2A. In the manufacturing apparatus 100, the tension of the laminated original film 2A between the first unwinding roll 110 and the winding roll 120 falls within the above range.

That is, one side of the manufacturing method of the laminated body of the present invention, with respect to the laminated film original cloth 2A, in the longitudinal direction includes adding 0.5N / mm ² or more and less than 50N / In a state of tension of ² mm, a coating film 60 is formed on the surface of the laminated film original cloth 2A, the aforementioned coating film is hardened, and an adhesion layer is formed on one side of the laminated film original cloth 2A.

When the tension of the laminated film original fabric 2A is 0.5 N / mm ² or more, the thickness of the formed coating film 60 is uneven, so it is difficult for the laminated original fabric 1A to form a wrinkle, and it is difficult to cause appearance defects. In addition, when the tension added to the laminated film original cloth 2A is less than 50 N / mm ² , it is difficult to destroy the film layer even if the laminated body 1 is added, and it is easy to maintain the gas barrier property.

From the laminated original fabric 1A manufactured as described above, for example, the laminated body 1 can be obtained by unwinding from the winding roll 120 and cutting each of them to a specific length in a direction intersecting with the longitudinal direction.

That is, the method for manufacturing a laminated body of the present invention may include, as one side surface, cutting the original laminated cloth 1A formed by the aforementioned manufacturing steps further in a direction intersecting with a longitudinal direction.

The manufacturing method of the laminated body of this embodiment is comprised as mentioned above.

According to the manufacturing method of the laminated body comprised as mentioned above, the manufacturing method of the laminated body which can suppress the damage of the thin film layer which has gas-barrier property, or generation | occurrence | production of an appearance defect can be provided.

(Modification)

FIG. 6 is an explanatory diagram showing a modified example of the above embodiment, and corresponds to FIG. 4 of the first embodiment. The manufacturing apparatus 300 shown in FIG. 6 includes a first unwinding roll 110, a second unwinding roll 130, a bonding roll 140, a surface treatment apparatus 150, a transport roll 180, and a cutting apparatus 190.

The conveying roller 180 is arranged on the downstream side of the laminating roller 140 on the conveying path of the laminated film original fabric 2A (laminated original fabric 1A). The conveying roller 180 has a pair of rollers 181 and 182, and the laminated original fabric 1A is held between the pair of rollers 181 and 182 and is conveyed to the downstream side.

The cutting device 190 is arranged on the conveying path of the laminated film original fabric 2A (laminated original fabric 1A) on the downstream side of the conveying roller 180. cut The cutting device 190 cuts the laminated original fabric 1A to a specific length in a direction that intersects the longitudinal direction of the laminated original fabric 1A, and continuously manufactures the laminated body 1.

In the manufacturing method of the laminated body using the manufacturing device 300 as described above, the cutting device 190 is used to perform the step of cutting the laminated raw fabric 1A to produce the laminated body 1. The winding roll 120 shown in FIG. 4 is not rolled. The laminated body 1 can be continuously produced by winding the laminated body original cloth 1A.

That is, one side of the method for manufacturing a laminated body of the present invention includes a winding roll 120 that does not wind the laminated original fabric 1A, but uses a cutting device 190 to cut the laminated original fabric 1A to produce a laminated body 1 The steps.

In addition, in the manufacturing apparatus 200 shown in FIG. 5 of the second embodiment, instead of the winding roll 120, the manufacturing apparatus 200 may be provided on the downstream side of the curing apparatus 170 as the manufacturing apparatus in which the above-mentioned conveying roller 180 and the cutting device 190 are arranged. Even if it is a manufacturing method of the laminated body using such a manufacturing apparatus, the laminated body 1 can be manufactured continuously.

〔Organic EL Device〕

FIG. 7 is a schematic diagram of an organic EL device using a laminate manufactured by the method for manufacturing a laminate according to this embodiment.

The organic EL device 1000 shown in the figure includes a substrate 1100, an organic EL element 1200 provided on the substrate 1100, and a laminate 1 provided on the substrate 1100 and the organic EL element 1200. The laminated body 1 was manufactured using the manufacturing method of the laminated body mentioned above.

The substrate 1100 is an organic EL element 1200 from the substrate 1100 In the case of a bottom emission type in which light is taken out side by side, a light transmissive one is used. When the organic EL element 1200 has a top-emission structure in which light is taken from the side opposite to the substrate 1100 side, the substrate 1100 may have light transmittance or may be opaque.

Examples of the material for forming the opaque substrate include ceramics such as alumina and resin materials. Alternatively, a substrate such as a surface of an insulating metal plate may be used. Examples of the light-transmitting substrate forming material include inorganic materials such as glass and quartz; and resin materials such as acrylic resin and polycarbonate resin. Among these, when the substrate is formed of a resin material, it is preferable to perform an appropriate gas barrier treatment.

The substrate 1100 may be one having flexibility, or one having no flexibility.

The organic EL element 1200 includes an anode 1210, a cathode 1220, and an organic light emitting layer 1230 supported by the anode 1210 and the cathode 1220.

The anode 1210 is formed of a commonly known forming material such as indium tin oxide, indium zinc oxide, and tin oxide.

The cathode 1220 is formed of a material having a smaller work function (for example, less than 5 eV) than the anode 1210. Examples of the material for forming the cathode 1220 include metal fluorides such as calcium, magnesium, sodium, lithium metal, and calcium fluoride; metal oxides such as lithium oxide; and organic metal complexes such as Acetylacetonato calcium. Things. When the organic EL element 1200 has a top-emission structure, the thickness or material of the cathode 1220 is selected so that the cathode 1220 has light transmittance.

The organic light emitting layer 1230 may be a material for forming an organic EL device, and generally known light emitting materials can be used. The material for forming the organic light emitting layer 1230 may be a low molecular compound or a high molecular compound.

The laminated body 1 faces the organic EL element 1200 and the substrate 1100 and the organic EL element 1200 with the adhesive layer 6 and then seals the organic EL element 1200 in a space surrounded by the laminated body 1 and the substrate 1100. In the figure, only a cross-sectional view in one direction is shown, but the organic EL element 1200 surrounds the laminated body 1 and the substrate 1100 in all directions.

In the organic EL device 1000 configured as described above, since the above-mentioned laminated body 1 is used, the organic EL element 1200 is sealed, and the thin film layer having gas barrier properties is difficult to be broken, and it is highly reliable. Moreover, in the laminated body 1 used, it becomes a person with a favorable external appearance by suppressing the occurrence of a defective appearance. Furthermore, when the organic EL device 1000 is an organic EL device 1200 having a top emission type, although the emitted light passes through the laminated body 1 and is emitted to the outside, the laminated body 1 suppresses the formation of the wrinkle of the adhesive layer 6 and the emitted light does not proceed Refraction. Scatter, but it is more effective when it is emitted to the outside.

As mentioned above, although referring to the attached drawing, and explaining the example of a form suitable for implementing this invention, it can be said that it is not limited to the example concerning this invention. Many shapes, combinations, and the like of each constituent member shown in the above-mentioned example are examples, and various changes can be made according to design requirements within a range not departing from the gist of the present invention.

For example, in the above embodiment, the step of forming the adhesive layer is performed in a state where tension is added to the laminated film original fabric 2A or the adhesive film 8A in the longitudinal direction, but the direction of adding the amount of force is not limited to this. apart from The longitudinal direction can be used to add tension to the laminated film original cloth 2A or the adhesive film 8A in a manner to spread to the width direction, and also to add tension to the biaxial direction of each film to implement the step of forming an adhesive layer.

[Example]

Although the present invention is described below by examples, the present invention is not limited to these examples.

[Laminated film]

The following examples and comparative examples use laminated films produced by the following methods.

The laminated film was manufactured using the manufacturing apparatus shown in FIG. 3 described above.

A biaxially-drawn polyethylene naphthalate film (manufactured by Teijin DuPont Film Co., Ltd., PQDA5, thickness 100 μm, width 700 mm) was used as a substrate, and this was placed in a delivery roller in a vacuum chamber. After the inside of the vacuum chamber is set to 1 × 10 ^-3 Pa or less, the substrate is transported at a constant speed of 0.5 m / min, and a thin film layer is formed on the substrate. The biaxially-stretched polyethylene naphthalate film used for the substrate is an asymmetric structure with easy-to-adhesion treatment (primer treatment) on one side, and a film layer is formed on the side without easy-to-adhesion treatment. . In a plasma CVD apparatus used to form a thin film layer, a plasma is generated between a pair of electrodes, which is in close contact with the surface of the electrode, and a substrate is transported to form a thin film layer on the substrate. In addition, the foregoing pair of electrodes has a magnetic flux density that is as high as the surface of the electrode and the substrate. A magnet is disposed inside the electrode, and when the plasma is generated on the electrode and the substrate, the plasma is restricted by high density.

Through the film formation of the thin film layer, the hexamethyldisilazane gas was introduced into 100 sccm (Standard Cubic Centimeter per Minute, 0 ° C, 1 barometric pressure), and the oxygen gas was introduced into 900 sccm facing the space between the electrodes forming the film forming area. An AC power of 1.6 kW and a frequency of 70 kHz is supplied between the electrode rollers and discharged to generate a plasma. Next, after the pressure of the exhaust port around the vacuum chamber is adjusted to 1 Pa, the amount of exhaust gas is adjusted, and then a thin film layer is formed on the transport substrate by a plasma CVD method. Repeat this step 4 times.

The film thickness of the thin film layer of the laminated film was obtained by measuring the step difference between the non-film forming part and the film forming part using Surfcorder ET200 manufactured by Kosaka Research Institute. The film thickness of the thin film layer of the obtained laminated film was 700 nm.

The total light transmittance of the laminated film was measured by a direct-reading haze computer (type HGM-2DP) manufactured by Suga Test Machine Co., Ltd. After the background measurement was performed in a sample-free state, the laminated film was set in a sample holder and measured. The total light transmittance of the obtained laminated film was 87%.

The water vapor transmission rate of the laminated film was determined by a calcium corrosion method (method described in Japanese Patent Application Laid-Open No. 2005-283561) under the conditions of a temperature of 40 ° C and a humidity of 90% RH. The water vapor transmission rate of the obtained laminated film was 2 × 10 ^-5 g / m ² / day.

The obtained laminated film is in a region of 90% or more of the film thickness direction of the thin film layer, from a relatively large atomic ratio to oxygen, silicon, and carbon. In order, the carbon distribution curve has an extreme value of 10 or more in the film thickness direction, and the absolute value of the difference between the maximum value and the minimum value of the carbon atomic ratio in the carbon distribution curve is 15at% or more.

In addition, XPS depth profiling was performed on the obtained laminated film under the following conditions to obtain the distribution curves of the obtained silicon atoms, nitrogen atoms, oxygen atoms, and carbon atoms. 8 is a graph showing a silicon distribution curve, an oxygen distribution curve, a nitrogen distribution curve, and a carbon distribution curve of the thin film layer of the laminated thin film 1 obtained in Production Example 1. FIG.

<XPS depth analysis measurement>

Etching ion species: Argon (Ar ⁺ )

Etching speed (equivalent value of SiO ₂ thermal oxide film): 0.05nm / s

Etching interval (SiO ₂ conversion value): 10nm

X-ray photoelectron spectrometer: Thermo Fisher Scientific Corporation, model name "VG Theta Probe"

X-ray irradiation: single crystal AlKα

X-ray spot and its size: 800 × 400 μm oval.

[Example 1]

The laminated film and the transparent double-sided adhesive tape (made by Lindec, TL-430S-06, 30 μm thick) were added with the following tensions, respectively, and laminated with a roller to produce the laminated body of Example 1. . At this time, a transparent double-sided adhesive tape is laminated on the film layer side of the laminated film.

Still, the transparent double-sided adhesive tape is equivalent to the above-mentioned embodiment. In the "adhesive film 8A", the adhesive layer of the transparent double-sided adhesive tape corresponds to "adhesive layer 6A" and "adhesive layer 6" in the above embodiment.

(Fitting conditions)

Tensile force per unit cross-sectional area of laminated film: 39N / mm ²

Tensile force per unit cross-sectional area of transparent adhesive double-sided tape: 0.1N / mm ²

[Example 2]

A laminate was produced in the same manner as in Example 1 except that the bonding conditions were changed to the following conditions.

(Fitting conditions)

Tensile force per unit cross-sectional area of laminated film: 0.5N / mm ²

Tensile force per unit cross-sectional area of transparent adhesive double-sided tape: 0.1N / mm ²

[Comparative Example 1]

A laminated body of Comparative Example 1 was produced in the same manner as in Example 1 except that the bonding conditions were changed to the following conditions.

(Fitting conditions)

Tensile force per unit cross-sectional area of laminated film: 62.5N / mm ²

Tensile force per unit cross-sectional area of transparent adhesive double-sided tape: 0.1N / mm ²

[Comparative Example 2]

A laminated body of Comparative Example 2 was produced in the same manner as in Example 1 except that the bonding conditions were changed to the following conditions.

(Fitting conditions)

Tension per unit cross-sectional area of laminated film: None

Tensile force per unit cross-sectional area of transparent adhesive double-sided tape: 0.1N / mm ²

The obtained laminate was evaluated by the following method.

(Evaluation 1: appearance observation)

The appearance of the obtained laminate was evaluated visually.

(Evaluation 2: Impact resistance test)

From the obtained laminate, a 2 cm square was cut out to prepare a test piece. The test piece was placed on the test table with the laminated film side down and the transparent double-sided adhesive tape side up, and an iron ball (diameter: 1 inch (2.54cm), weight, : 68g) plus punch.

The laminated body after falling the ball was observed at a magnification of 210 times using a microscope (manufactured by High Rocks Co., Ltd., DIGITAL MICROSCOPE KH7700), and the number of cracks of the thin film layer existing in the field of view of 1.8 mm × 1.4 mm was measured.

The evaluation results are shown in Table 1 below. In Table 1, "A" is shown as a non-defective product as a non-defective product, and "B" is used as a non-defective product as a non-defective product. Again 1. Indicate the transparent double-sided adhesive tape used as "adhesive tape".

As a result of the evaluation, in the laminates of Examples 1 and 2, there was no wrinkle after bonding, and in the film layer after the impact test, there was no crack in the observation field.

In addition, in the laminated body of Comparative Example 1, although there was no wrinkle after bonding, in the film layer after the impact test, cracks were observed in 14 of the observation fields.

Moreover, in the laminate of Comparative Example 2, the film layer after the impact test was observed, although no cracks were observed in the visual field, wrinkles were formed on the transparent double-sided tape.

From the above results, it is understood that the present invention is useful.

Claims (8)

A method for manufacturing a laminate, which is a method for manufacturing a laminate having a laminate film and an adhesive layer formed on a side of the laminate film, and the laminate film has a laminate substrate and at least silicon. A thin film layer formed between the substrate and the adhesive layer. The method for producing the laminated body has the laminated film as a continuous continuous laminated film original fabric in the form of a strip, and is transported in the longitudinal direction. The laminated film original fabric is in a state where a tension per unit cross-sectional area of 0.5 N / mm ² or more and less than 50 N / mm ² is added to the side of the laminated film original fabric in the longitudinal direction. Forming the aforementioned bonding layer. For example, in the method for manufacturing a laminated body according to claim 1, the material for forming the adhesive layer is a strip-shaped continuous adhesive layer original fabric. In the step of forming the adhesive layer, the adhesive layer original fabric is transported in the longitudinal direction, and Next, a layer of original fabric is bonded to the layered film original fabric in a state where a tension per unit cross-sectional area of 0.01 N / mm ² or more and less than 5 N / mm ² is added in the longitudinal direction. For example, if the method for manufacturing a laminated body according to claim 1 or 2, the steps include that the aforementioned substrate is to continuously transport a strip-shaped continuous substrate raw fabric, and that the substrate is continuous on at least one side of the substrate raw fabric. The aforementioned thin film layer is formed. In the method for manufacturing a laminated body according to claim 3, wherein the step of forming the film layer is performed by using a first film forming roller that is used to wind the base fabric, and paired with the first film forming roller. An AC voltage is applied between the second film-forming roll that winds the base material original cloth to generate a space between the first film-forming roll and the second film-forming roll. The film-forming material is the film-forming material. Gas discharge plasma plasma CVD. The method for manufacturing a laminated body according to claim 4, wherein the discharge plasma is formed by forming an AC electric field between the first film forming roller and the second film forming roller, and simultaneously forming the first film forming roller and the foregoing film. The second film-forming roll expands in an endless tunnel-shaped magnetic field in the opposing space, and includes a first discharge plasma formed along the tunnel-shaped magnetic field and a second discharge plasma formed around the tunnel-shaped magnetic field. The step of forming the thin film layer by the slurry is to carry the substrate base cloth in such a manner that the first discharge plasma and the second discharge plasma overlap each other. The method for manufacturing a laminate according to claim 4, wherein the thin film layer includes at least silicon, oxygen, and carbon, and the step of forming the thin film layer includes the step of forming the thin film layer from the surface of the thin film layer. The total number of silicon atoms, oxygen atoms, and carbon atoms contained in the thin film layer relative to the point located at the aforementioned distance represents the ratio of the number of silicon atoms (the ratio of the number of silicon atoms) and the ratio of the number of oxygen atoms, respectively. (The ratio of the number of atoms of oxygen) and the ratio of the number of carbon atoms (the ratio of the number of atoms of carbon) in the silicon distribution curve, oxygen distribution curve, and carbon distribution curve to satisfy the following conditions (i) to (iii) Way to regulate the mixing ratio of the organic silicon compound and oxygen contained in the film-forming gas: (i) the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are among the entire film thickness of the thin film layer The area of 90% or more satisfies the conditions represented by the following formula (1), (atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon). ． ． (1); (ii) the carbon distribution curve has at least one extreme value; (iii) the absolute value of the difference between the maximum value and the minimum value of the carbon atomic ratio of the carbon distribution curve is 0.05 or more. For example, the method for manufacturing a laminate according to claim 6, wherein the absolute value of the difference between the maximum value and the minimum value of the silicon atomic ratio in the silicon distribution curve of the thin film layer is less than 5 at%. The method for manufacturing a laminated body according to claim 1 or 2, wherein the composition of the thin film layer is SiO _x C _y (0 <x <2, 0 <y <2).